JPS6025379B2 - Lower glaze frit composition for steel plate enameling - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lower citrus frit composition for steel plate enamel that does not contain fluorine and atomic compounds.

Conventionally, many of the lower yuzu frit compositions for enameled steel plates contain fluorine, fluorine compounds, and the like.

In frits for steel sheet enameling, fluorine and fluorine compounds are used as a flux during frit manufacturing to promote the melting of the compound, and during enameling firing, they serve as low-melting components to reduce the melting of the frit and give the enameled one a good gloss. This is because it has a remarkable effect of giving. however,
Fluorine and fluorine compounds are extremely toxic and are unfavorable in terms of pollution because they are dispersed more thinly into the air than in the frit composition during frit manufacturing or enamel firing. The frit composition for steel plate enamel of the present invention does not contain any of these highly toxic chemical elements and fluorine compounds, but can be used in steel plate enamels as described below for secondary vessels containing fluorine and fluorine compounds. This is an excellent Shimotsumugi frit composition for steel plate enamel that has frit meltability, enamel low melting property, and gloss that are equal to or higher than those of the Yuri frit composition, and it contains Si02, Ti02,
31 to 72% of one or more of Z2, Sn02 containing at least Si02, 11 to 42% of &03, and Li
12 to 37% of one or more of Na20, K20, and Na20 (however, if the total amount is 100%, Na2045% or more, Li2025% or less, K
2050% or less) and 100 parts by weight of the main component, A203 is 12% or less, Ca○, Ba0, Zn○
, Mg○, Sr○ at least one or more from 1 to 22
% (however, each is less than 12%), Moo3, V20
5, P2Q, S et al. 03 containing at least one species containing Moo3 in an amount exceeding 0% but not more than 7% and Coo, Ni○
, Cu○, Mn02, and Fe203 in an amount of 7 to 42 parts by weight as a subcomponent consisting of 0.5 to 10% of at least one of the following.

That is, in the present invention, '1}Si02, Ti02, Zte0
2, a predetermined amount of at least one kind of Sn02, including at least Si02, {2} a predetermined amount of B2Q, and {3} Li20.
, K20, 1 containing at least Na20 among Na20
For the main component consisting of a specified amount of seeds or more, ■Aso203
Below the specified amount, '5}Ca○, Gender 0, Zn○,, Mg○
, a predetermined amount of at least one kind of S, '6}MO
At least Mo among O3, V2Q, P2Q, SQ03
a predetermined amount of one or more types including o3 and '7)Coo''Nj
The synergistic effect of containing a predetermined amount of at least one of O, Mn02, and Fe203 in a specific ratio, and in particular, the inclusion of Moo3, Na20, etc. as essential components, makes it possible to reduce fluorine and fluorine compounds. As mentioned above, we have found a frit composition that has excellent properties such as melting properties, low melting properties, and gloss even when it does not contain. As main components, Si02, Ti02, Z2, S
31 at least one type of n02 containing at least Si02
~72%, preferably 35-66%, B203 from 11 to
41% preferably 12-39% and Li20, K20
, Na20, it is important to contain 12 to 37% of at least one kind containing Na20, preferably 13 to 35% of two or three kinds containing Li20 and Na20.

In other words, at least one of Si02, Ti02, Z2, and Sn02, including at least Si02, is a basic component of the frit, and if the content exceeds 72%, the melting temperature of the frit will be high. , a high firing temperature is required, making it difficult to obtain a glossy and smooth enamel.

On the other hand, if Si02 etc. is contained less than 31%,
The frit composition is not chemically stable. Also, &0
If the B03 content is less than 11%, the firing temperature will be too high, and if the B03 content exceeds 41%, the frit composition will not be chemically stable. Furthermore, Li20
, K20, 1 containing at least Na20 among Na20
If the content is less than 12%, the firing temperature is too high and the coefficient of thermal expansion is too small, resulting in large deformation when the steel plate is enameled. If the content exceeds 37%, it is not chemically stable. This is because the enamel will not form a frit composition and the coefficient of thermal expansion will be too large than that of the steel plate, causing the enamel to separate from the steel plate.

Here, when the total amount of one or more of Li20, K20, and Na20 is taken as 100%, Na20 is 45%, preferably 55% or more, Li20 is 25% or less, preferably more than 0% and 16% or less, and K20 is 50%. % preferably 40% or less, but if it contains less than 45% of Na20, more than 50% of K20, and more than 25% of Li20, the firing temperature will increase.
This is because the appearance of the enamel deteriorates. Also, one of the subcomponents
The species A2Q is 12% or less, preferably 3 to 10%
It is preferable to include A-203 in order to widen the firing temperature range of the enamel and to improve the mechanical strength.When A-203 is contained in an amount exceeding 12%, the melting temperature of the frit is high and the firing temperature is high. is undesirable because it increases the gloss of the enamel and deteriorates its luster. Also Ca0, gunwale 0,
1 to 2 of at least one of Z, Mg0, and S
It is preferable to contain 2%, preferably 2 to 18%, because it widens the firing temperature range of the enamel and prevents the enamel from running out of phosphorus.If it is less than 1%, the firing temperature range is narrow and This is because it is easy to break, and if the content exceeds 22%, the fired appearance will be poor. In this case, C
Each of a○, Ba○, Zn○, Mg0, Sr○ is 12%
It is necessary that the amount is below 12%, because if the content exceeds 12%, the firing temperature will increase and the fired appearance will deteriorate. Furthermore, MOO3, V2
At least MOO3 among 05, P205, Sb203
It is extremely important to contain more than 0% and preferably 5% or less of one or more of the following in order to lower the surface tension, thereby making the enamel surface smooth and increasing its gloss. However, if the content exceeds 7%, the firing temperature range becomes narrow and the fired appearance deteriorates, which is not preferable. The reason why Moo3 is an essential component is that it is an essential component for improving the fired appearance, especially gloss and smoothness, and lowering the firing temperature. C
0.5 to 10%, preferably 1 to 7% of at least one of Ni0, Cu○, MN02, and Fe203
Containing it is an essential component that imparts adhesion of the enamel to the steel plate, and if it is less than 0.5%, the effect is insufficient and the enamel may peel off from the steel plate after firing, so it is not preferable. This is because if the content exceeds %, the fired appearance will deteriorate. And the main component 10
It is necessary to contain the subcomponents in a total amount of 7 to 42 parts by weight, preferably 11 to 37 parts by weight, based on 0 parts by weight. The main component is the basic component of the frit composition, that is, it is an essential component for the frit to become enameled glass.However, the main component alone is approximately 900% or less, which can be produced into the steel sheet required as the enameled glass. It does not have characteristics such as temperature, firing temperature range, fired appearance, adhesion, etc., and it is necessary to contain a predetermined amount of subcomponents.If the subcomponents are contained in excess of 42 parts by weight, The frit composition will not be formed, and the fired appearance will be poor. Furthermore, if the content is less than 7 parts by weight, the firing temperature will increase and the firing temperature range will become narrower, which is not preferable. Next, the production of the lower pongee frit composition for steel plate hollows of the present invention and the method for producing steel plate hollows using the same will be described.

That is, the raw materials are calculated, weighed, and mixed so that each component of the crude frit composition for steel plate hollowing according to the present invention has a predetermined composition, and then melted at a temperature of 1,100 to 125,000 for about 1 hour to decompose and melt the raw materials. After homogenizing the material, it is immersed in water, rapidly cooled, dried, and fritted. Furthermore, an enamel using the frit composition of the present invention can be manufactured in the same manner as a normal steel plate enamel. That is, the mill formulation shown in Table 1 is carried out, and the mixture is pulverized using a ball mill or the like to prepare a slip. Table 1 Next, pongee is applied using a spray gun or the like so that the thickness of the enamel after firing is 70 to 90 m on a steel plate that has undergone normal pretreatment, and after drying, it is heated at a temperature of 700 to 88,000 ℃. It is fired for about 1 to 4 minutes to obtain an enamel steel plate.

Next, examples of the lower pongee frit composition for steel plate enamel of the present invention will be described.

Each raw material was weighed and mixed so as to have the composition shown in Table 3, melted at 1200 qo for 1 hour, and then poured into water to obtain a frit composition of the present invention. This frit composition was subjected to the mill formulation shown in Table 2, and then placed on a steel plate with a thickness of 0.8 mm and a size of 10×1 ratio so that the enamel thickness after firing would be 70 mm. The vessels shown in Table 3 were sprayed with a spray gun and fired for 3 minutes at the temperatures listed in Table 3. 1~No. 60 steel plate enamel products were obtained. Table 2: Reference product No. 2 for comparison. 61~No. 68 and conventional product M. 69～earth. 72 was also prepared.

The glossiness, smoothness, adhesion, etc. of each of the obtained enamel steel plates were compared and measured, and the results are shown in Table 3.

In the measurement, the glossiness was expressed as the average value of 5 measured values measured at an incident angle of 60 degrees using a digital gloss meter ○M-Fsune manufactured by Murakami Color Research Institute. Surface assembly is JIS standard B 060
The ten-point average roughness of the surface roughness test method No. 1 is displayed. In addition,
The standard length was 2.5 ribs. In addition, the adhesion is determined by ASTM
Adhesion index (%) according to the adhesion test method of standard C 313
It was displayed in As is clear from Table 3, the enameled steel plate using the frit composition of the present invention has the same gloss, smoothness, and adhesion as conventional products containing fluorine and fluorine compounds, or It was confirmed that the performance exceeded that level.

In addition, Shimoyuzu frit for steel plate enamel is often used by mixing several types of frits with different compositions.

Usually, in this case, frits with different firing temperatures are used, but it goes without saying that the frit compositions of the present invention can also be used in combination. Note that the component range of the enamel composition of the present invention and the composition range of the Examples in Table 3 are shown in comparison on a ternary diagram as shown in FIGS. 1 and 2. As described above, the Shimotsumugi frit composition for steel plate enamel of the present invention does not contain any harmful fluorine or fluorine compounds unlike conventional products, but the synergistic effect of each component contained,
In particular, by containing specific amounts of Moo3, Li20, Na20, etc., it has meltability, low wisteria, gloss, smoothness, and adhesion that are equivalent to or higher than conventional frit compositions containing fluorine and fluorine compounds. It can be used as a pongee frit for hollow steel plates, and is extremely useful industrially. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a composition diagram showing a comparison of the component range of the enamel composition of the present invention and the composition range of the examples in Table 3 on a ternary diagram, and FIG. It is a composition diagram showing the range of the enamel composition on a ternary diagram of Na20, Li20, and K20 and comparing it with the composition of the example in Table 3.

Figure 1 Figure 2

Claims (1)

[Claims] 1 SiO_2, TiO_2, ZrO_2, SnO_2
31 to 7 of at least one type containing at least SiO_2
2% by weight, 11-42% by weight of B_2O_3 and Li
At least Na_2O, K_2O, Na_2O
12 to 37% by weight of one or more types containing 2O (however, if the total amount is 100% by weight, 45% by weight or more of Na_2O,
(Li_2O25% by weight or less, K_2O50% by weight or less)
For 100 parts by weight of the main component consisting of
12% by weight or less of 3, CaO, BaO, ZnO, MgO
, SrO in an amount of 1 to 22% by weight (
However, each component is 12% by weight or less), MoO_8, V_2
O_5, P_2O_5, Sb_2O_3, one or more containing at least MoO_3 exceeding 0% by weight and 7% by weight or less, and CoO, NiO, CuO, MnO_2, F
0.5 to 10 of at least one of e_2O_8
1. A lower glaze frit composition for steel plate enamel, characterized in that the composition contains 7 to 42 parts by weight of subcomponents consisting of 7 to 42 parts by weight.